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Volumn 21, Issue 35, 2015, Pages 12279-12284

A Striking Case of Enantioinversion in Gold Catalysis and Its Probable Origins

Author keywords

density functional calculation; enantioinversion; gold; heterogeneous catalysis; phosphoramidites

Indexed keywords

CATALYSIS; CYCLIZATION; DENSITY FUNCTIONAL THEORY; FREE ENERGY; GOLD;

EID: 84939470244     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201502160     Document Type: Article
Times cited : (27)

References (81)
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    • For a more comprehensive data set and a selection of other substrates, see the Supporting Information.
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    • Although CH2Cl2 gives somewhat lower ee's than EtOAc, it was used in all mechanistic investigations because it is more readily dried; recall that trace amounts of water in EtOAc exert a massive influence (Table 2, entries 1 and 2).
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    • See the Supporting Information for details; the PBE0-D3//TPSS-D3 combination was shown to provide realistic geometries and energies for related gold systems in benchmark studies, cf
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    • For the sake of CPU-time, the second substrate molecule was modeled by 2,2-dimethyl-1-propanol. The branching at the β position to the hydroxyl group is similar to that in the substrate. The structural differences beyond the β position are outside the catalyst cavity and are thus not anticipated to lead to qualitatively different results.
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    • For the corresponding energy profiles of the pathways in a protic medium, with an explicit methanol molecule included at each stationary point, see the Supporting Information
    • For the corresponding energy profiles of the pathways in a protic medium, with an explicit methanol molecule included at each stationary point, see the Supporting Information.
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    • For studies on gold catalyzed reactions featuring counterion participation in proton transfer, see
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    • Attempts to underpin this assumption by NMR using the methyl ether 2-OMe as a dummy substrate were inconclusive but certainly not in contradiction. For BF4-, 19F/1H HOESY experiments with different mixing times and over a broad temperature range showed no detectable intermolecular cross-relaxation correlations, which suggests that there is no tight association of the escorting counterion; in contrast, heteronuclear NOEs between F3CCOO- (19F) and the ligand (1H) show that this anion resides in the binding pocket, at or closely associated to the gold atom. Unfortunately, the dynamic nature of this system prohibits detection and structural analysis of the loaded complex by NMR
    • Attempts to underpin this assumption by NMR using the methyl ether 2-OMe as a dummy substrate were inconclusive but certainly not in contradiction. For BF4-, 19F/1H HOESY experiments with different mixing times and over a broad temperature range showed no detectable intermolecular cross-relaxation correlations, which suggests that there is no tight association of the escorting counterion; in contrast, heteronuclear NOEs between F3CCOO- (19F) and the ligand (1H) show that this anion resides in the binding pocket, at or closely associated to the gold atom. Unfortunately, the dynamic nature of this system prohibits detection and structural analysis of the loaded complex by NMR.
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    • 2-OMe is not totally unreactive but eventually rearranges to a mixture of 1,3-diene isomers
    • 2-OMe is not totally unreactive but eventually rearranges to a mixture of 1,3-diene isomers.
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    • Boltzmann averaging of the computed chemical shifts for C(1), C(2) and C(3) of the allene moiety leads to much better agreement with the experimental values than comparisons for any individual isomer; for details see the Supporting Information
    • Boltzmann averaging of the computed chemical shifts for C(1), C(2) and C(3) of the allene moiety leads to much better agreement with the experimental values than comparisons for any individual isomer; for details see the Supporting Information.
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    • The pathway via complexation of the much less accessible π-faces has also been computed but can safely be disregarded; for details see the Supporting Information
    • The pathway via complexation of the much less accessible π-faces has also been computed but can safely be disregarded; for details see the Supporting Information.
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    • Independent of this naphthyl flip is an additional rotameric process involving the amine part of the phosphoramidite ligand scaffold which is fast (ms time scale at -20 °C) and obviously quite unhindered by the naphthyl groups or the bound allenol. We had already previously implied such a process in the loading of the chiral complexes, where the rotational freedom of the P-N bond allows the amine to give way to the incoming substrate, see ref. [5]
    • Independent of this naphthyl flip is an additional rotameric process involving the amine part of the phosphoramidite ligand scaffold which is fast (ms time scale at -20 °C) and obviously quite unhindered by the naphthyl groups or the bound allenol. We had already previously implied such a process in the loading of the chiral complexes, where the rotational freedom of the P-N bond allows the amine to give way to the incoming substrate, see ref. [5].
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    • For enantioreversion by solvent change using a phosphoramidite with a biphenyl backbone, see
    • For enantioreversion by solvent change using a phosphoramidite with a biphenyl backbone, see:, H. Yu, F. Xie, Z. Ma, Y. Liu, W. Zhang, Org. Biomol. Chem. 2012, 10, 5137-5142.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.